Process of treating ammoniacal liquors



Nov. 18, 1930.

D. R. MEANS 1,781,987

PROCESS OF TREATING AMMONIACAL LIQUORS Filed Sept. 20, 1926 a. .7 "za I Patented- Nov. 18, I930 UNITED {STATES (PATENT oar-Ice DWIGHT B. MEANS, OI HADENA. COUNTY, OHIO, ASSIGNOR TO PITTSBURGH PLATE GLASS COMPANY, A CORPORATION OF PENNSYLVANIA.

PROCESS OF TREATING AMMONIAOAI: LIQUOBS Application fl1ed= September 20,1926. Serial No. 130,542.

The invention relates to a process of distilling ammonia from solutions where lime is necessary to free the ammonia, an example being the distillation of ammonia .in the ammonia soda process. Here, the liquor contains large amounts of ammonium carbonate and ammonium chloride.

CO driven off, after which milk of lime is added to decompose the ammonium chloride, and the ammonia is distilled off with steam. The milk of lime carries a large amount of water, usually 70 to 80 per cent, which must lie heated either before or after entering. the distilling apparatus. One object of the Present invention is the saving of the heat required for heatin the water in the milk of lime. Another ob ect is to still'further'economize in the heat required in the distiller by utilizing the heat liberated in the slacking of the quick lime which is used in the improved process in place of the milk of lime; the procless in this respect also involving a saving over that of my copending applicatlon, Serial No.

136,540, filed on even date herewith inwhich dry hydrated lime is employed. The present process also involves an improvement .over that of my copending application, Serial No. 136,541 filed on even date herewith which discloses the use of pulverized quick lime, in that the present process avoids the grinding .or.

pulverizing of the quick lime, thus reducing the cost and leavin the unburn ed stone unground, so that it is possible tm recover this stone mg returnit to the kiln for burning, This is important in the ammonia process, where in order to get a high per cent of CO in the gas from the lime k1lns, such kilns are .usually operated to givea'hi'gh per cent, 5 to 12 per cent, of unburned stone in the lime.

, The loss of this much stone would be a serious one. One form of apparatus for treating the ammoniacal liquor preliminary to distillation is shown in the accompanying drawing,

I wheren:

The figurels a diagrammatic side elevation partly in section.

. In carrying out-the process, an ammoniacal liquid, such as that from the ammonia soda process containing ammonium chloride (the The carbonate is. broken up by the application of heat and the consists of the sma cold water sprays ammonium carbohate having been driven off by heat through the application of steam) is conducted into the tank 1 through the pipe 2 and then carried to the distilling apparatus or still 3 through the pipe 4. Quick lime is introduced into the tank from theconduit 5 pro .vided with the rotary feeder 6.. This feeder is divided into four or more sections and revolves in a close fitting housing. This type of feeder reduces the leakage of gas through the conduit to a minimum. The efiect of any leakage is also minimized by providing the suction line 7 to which an automatic vacuum regulator 17 Y is applied, and which maintains ably driven from the gear 11 at its upper en The lime supplied through the conduit -5 is caught by the upper tray, and is then raked therefrom by an agitator and falls by gravity to the next tray. The lime in this way gradually'works downward'and is slacked-and goes into solution or is suspended in the liquor.

Any of the material which reaches the bottom I i of the-tank is largely unburned stone and impurities which are picked up by a suitable elevator in the casin 12, such elevator, as shown, consisting ofa driven endless belt 12provided with suitable scoops or. cups. At the upper end'of the casing the materlal is discharged to a washer 13 from which the unburned stone may be recovered and transferred'to the'kiln for burnin w "Means 0% various kinds ire provided for reducing the loss of any ammonia passing in'to'the casing 12. One of these is a blow off pipe 14 leading from the pump 14, supplied with waste liquor from the blow off pipe 14 of the still. This washes the ammonia out to/a large extent. Since the liquor is hot, direct from the still, practically no heat willbe used in running a considerable vol ume through the still a'second time. The liquor can be sprayed'into the casing 12 if de-' sired. Another'means for reducing the loss of ammonia escapin through the casing 12 16 leading into the top of therasing. These sprays serve to wash the ammonia out of the vapor rising in the casingand return it to the liquor. i

' The washer 13, spray 16 and circulation of distilled liquor through pipe 14 are all intended to prevent the loss of ammonia either as a Vapor or as an absorbed liquor with the material being conveyed out. Under some conditions it will not be necessary, from an economical View point, to use all of them. For example, in most cases, the washer may be dispensed with. I

If the pressure in the still at the point 18 is materially above or below atmospheric pressure it might be necessary to install I pumps in lines 2 and 4 to insure a good flow and still maintain only a slight vacuum in the vessel 1. Under some operating conditions 20 it is desirable that the vessel 1 be maintained at only slightly below atmospheric pressure in order to prevent an excessive volume of air from being drawn in through the line feeder.

However, often it is an economic advantage .25 to operate the still 3 with a vacuum of two to ten inches of mercury. In the latter case,

liquor under some circumstances may not flow down through the pipe 2 to the tank 1 because of the difierence in pressurel When this occurs, it is necessary that the transfer be made with a pump.

In operation, liquor containing various ammonium compounds, but largely as ammonium carbonate, and ammonium chloride enters the top of the distiller through the pipe 19 and fiow's down through a suitable packing in the casing, such as coke, where it is acted upon by steam supplied through the pipe 20, and; flowing upward through the 40 casing. The packing coke referred to is the usual packing in distillation columns. Coke varying fromabout two to ten inches in size is introduced into the upper part of the still 3 so as to fill substantially the entire space extending from the ipe 18 to within two or three feet of the li or inlet 19. The heat breaks down the ammonium carbonate and .the steam carries ofi the carbon dioxide and ammonia resulting from the decomposition '50 of the carbonate. It is essential that this regrams per liter off-NH in the form'ofammonium chloride, about 1 gram per liter of ammonium sulphate, to 90 grams --per liter of sodium chloride, 10 to 20 grams per liter of NI-I in solution as ammonium hydroxide and less than 1 gram per liter of CO The ammonia present as the hydroxide probably is carried up into this liquor from the lower part of the still 3 during the process of fractional distillation. Ammonium car- 'bamate maybe formed. If it is, it is broken up by the steam and heat treatment and the result, CO is carried off with the ammonia and steam at the top of the apparatus; A small proportion of sodium chloride may be present but it is of relatively minor importance and, as stated, it-is only present in a small quantity and represents that portlon of the salt which has not been converted into sodium bicarbonate in 'the ammonia soda process. Liquor of the above character, which has been subjected to a steam treatment in the upper part of the still 3, is drawn from the still at 18 through the pipe'2, and passes into the mixing tank 1 wherethe lime is added to secure the decomposition of the ammonium chloride, forming calcium chloride and free ammonia. The liquid passes through the outlet pipe 4 to the still, or dis tiller, in the. lower portion of which the ammonia distills ofl", the calcium chloride remaining in solution and passing out at the bottom through the pipe 14" with other waste materials, such as, finely divided impurities from the-lime. o The gases coming off the-top of the still 3 will vary somewhat in temperature but usually they are held between and C. This is'usually regulated by the quantity of steam entering the bottom of the still 3. The pressure at the top of the still 3 usually varies from 0 to 10 inches of mercury vacuum but,

temperature of the liquid at the bottom 0t the'still 3 usually varies between 10Q and 115 C., depending on the vacuum carried at the top of the still. The pressure at the bottom of the still is usually from 0 to 8 pounds gage. due to the resistance through the still. The temperature in the mixing tank 1. may vary. )Satisfactory results have been obtained by using a temperature varying betweenQO and 105 o.

. What I claim is: 4

1. .The process of recovering ammonia.

from liquor containing fixed ammonium compounds including. ammonium chloride coma-- prisiiig supplying at one end of a mixer a quantity of unpulverized quick lime containing unburned lime stone in an amount necessary to decompose the fixed ammonium compounds, supplying countercurrently at a .re-

mote portion of the mixer ammoniacal liquor, allowing the unpulverized quick lime .'con-. taining the unburned limestone to gradually work downwardly and be suspended in the ammoniacal liquor and the unburnedlime stone to settle and segregate inthellower portion of the liquor, removing the unburned lime stone from the liquor,=and'subjecting the monium compounds includin liquor containing the lime suspension to distillation to recover ammonia therefrom.

2. The continuous process of recovering ammonia from liquor containing fixed amammonium chlorideand from which the ee ammonia has been. removed comprising supplying at one end of a mixer containing a serles of trays a quantity of unpulverized quick lime containing unburned lime stone'in a quantity 'sufiicient to decompose the fixed ammonium compounds, supplying countercurrently at the lower portion of the mixer animomacal liquor, feedin the unpulverized quick lime containing un urned lime stone to the first of the series of trays, ositively feeding said material to others. of said series of trays, whereby the quick lime gradually works downwardly in the mixer and enters into suspension in the ammoniacal liquor and the unburned lime stone segregates in the lower portion of the li uor, removin the unburned lime stone from t e liquor, an subjecting the liquor containing the lime suspension to dis- 3. The continuous process of recovering ammonia from liquor containing fixed ammonium compounds inclu ammonium chloride and from which the ee ammonia has been substantially removed comprising supplying at one end of a mixer a quantity of unpulverized quick lime contaimng unburned lime stone in an amount necessary to decompose the fixed ammonium compounds, supplying countercurrently at. the lower portion of the mixer ammoniacal liquor, positively feeding downwardly through the ammoniacal liquor the unpulverized quick lime containing the unburned lime stone, settling and segregating the unburned lime stone in t e lower portion of the liquor, removing the unburned lime stone from the liquor, re-

moving ammonia from the unburned lime stone by washing with waste liquor from the process, passin the partially purified lime stone to a was er for washing prior to reburning, and subjecting the lfillior containing the lime suspension to dis ation to' recover the ammonia therefrom.

4. The continuous process of recovering ammonia from'liquor containing fixed am? monium compounds including ammonium chloride from which the free ammonia compounds have been substantially removed comprising supplyingi at one end of a mixer containing a series of trays aquantity of unpulverized quick lime contamingunburned lime stone in a quantity sufiicient to decompose the fixed-ammonium compounds, suppl ing countercurrently at the lower portion 0 the mixer ammoniacal liquor, feedin the unpulverized quick lime containing an urned lime stone to the first of the seriw of trays, positively 'feeding said material to others of said i series of trays whereby the quick lime grad-..

tillation to recover the ammonia therefrom..'

ually works downwardly in the mixer and stone to awasher for washing prior to reburning, and subjecting the liquor containg the lime suspension to distillation to recover the ammonia therefrom.

5. The continuous process of recovering ammonia from liquor containing fixed ammonium compounds including ammonium chloride from which the free ammonia compounds have been substantially removed comprising'su plying at one end of a mixer a quantity 0 unpulverized quick lime contain- I ing unburned lime stone in an amount necessary todecompose the fixed ammonium compounds, supplying countercurrently at the lower portion of the mixer ammoniacal liquor, positively feeding downwardly through the ammoniacal liquor the unpulverized quick lime containing the unburned lime stone, settling and segregatingthe unburned lime stone in the lower portion of the liquor removing the unburned lime stone from the liquor, washing the same with waste liquor from the process prior to reburning and reuse in the process, and subjecting the liquor containing the lime suspension to distillation to recover the ammonia therefrom.

6. The continuous process of recovering ammonia from liquor containing fixed ammonium compounds including ammonium chloride from which tlfe free ammonia compounds have been substantially removed, comprising supplying at one end of a mixer containing a series of trays a quantity of unpulverized quick lime containing unburned lime stone in a quantity suflicient to decompose the fixed ammoniumvcompounds, supplying countercurrently at the lower portion of the mixer ammoniacal liquor, allowing the unpulverized quick lime containing unburned lime stone to the first of the series of trays,

positively feeding said material to others of said series of trays whereby the quick lime gradually :works downwardly in the mixer and enters into suspension in the ammoniacal liquor, and the unburned lime stone segregates in the lower portion of the liquor, removing theunburned lime stone from the liquor, washing the same with liquor from the process prior to reburning and'reuse in the process, and subjecting the liquor containing the lime in suspension to' distillation to recover the ammonia therefrom.

7. The continuous process of treating liquors containing fixed pounds from which free ammonia has been substantially removed-comprising positively feeding downwardly through the ammoniaammonium comcal liquor quick lime containing a quantity of unburned lime stone, the quick lime being suspended inthe liquor, settling and segregating the unburned lime stone, and subjectmg the liquor containing the lime in suspension to distillation to recover the ammonia therefrom, and washing the separated unburned lime stone with liquor from the process prior to reburning said lime stone for reuse in the process.

In testimony whereof, I have hereunto subscribed my name this 9th day of Sept, 1926.

v DWIGHT R. MEANS. 

